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Full-Text Articles in Life Sciences

Concerted Ho2 Elimination From Alpha-Aminoalkylperoxyl Free Radicals: Experimental And Theoretical Evidence From The Gas-Phase Nh2 Chco2 - + O2 Reaction, Gabriel Da Silva, Benjamin Kirk, Celli Lloyd, Adam Trevitt, Stephen Blanksby Jul 2013

Concerted Ho2 Elimination From Alpha-Aminoalkylperoxyl Free Radicals: Experimental And Theoretical Evidence From The Gas-Phase Nh2 Chco2 - + O2 Reaction, Gabriel Da Silva, Benjamin Kirk, Celli Lloyd, Adam Trevitt, Stephen Blanksby

Adam Trevitt

We have investigated the gas-phase reaction of the α- aminoacetate (glycyl) radical anion (NH2 •CHCO2−) with O2 using ion trap mass spectrometry, quantum chemistry, and statistical reaction rate theory. This radical is found to undergo a remarkably rapid reaction with O2 to form the hydroperoxyl radical (HO2 •) and an even-electron imine (NHCHCO2−), with experiments and master equation simulations revealing that reaction proceeds at the ion−molecule collision rate. This reaction is facilitated by a low-energy concerted HO2 • elimination mechanism in the NH2CH(OO•)CO2− peroxyl radical. These findings can explain the widely observed free-radical-mediated oxidation of simple amino acids to amides …


Gas-Phase Reactions Of Aryl Radicals With 2-Butyne: An Experimental And Theoretical Investigation Employing The N-Methyl-Pyridinium-4-Yl Radical Cation, Adrian Lam, Cong Li, George Khairallah, Benjamin Kirk, Stephen Blanksby, Adam Trevitt, Uta Wille, Richard O'Hair, Gabriel Da Silva Jul 2013

Gas-Phase Reactions Of Aryl Radicals With 2-Butyne: An Experimental And Theoretical Investigation Employing The N-Methyl-Pyridinium-4-Yl Radical Cation, Adrian Lam, Cong Li, George Khairallah, Benjamin Kirk, Stephen Blanksby, Adam Trevitt, Uta Wille, Richard O'Hair, Gabriel Da Silva

Adam Trevitt

Aromatic radicals form in a variety of reacting gas-phase systems, where their molecular weight growth reactions with unsaturated hydrocarbons are of considerable importance. We have investigated the ion–molecule reaction of the aromatic distonic N-methyl-pyridinium-4-yl (NMP) radical cation with 2-butyne (CH3C≡CCH3) using ion trap mass spectrometry. Comparison is made to high-level ab initio energy surfaces for the reaction of NMP and for the neutral phenyl radical system. The NMP radical cation reacts rapidly with 2-butyne at ambient temperature, due to the apparent absence of any barrier. The activated vinyl radical adduct predominantly dissociates via loss of a H atom, with lesser …


Attaching Molecular Hydrogen To Metal Cations: Perspectives From Gas-Phase Infrared Spectroscopy, Viktoras Dryza, Berwyck Poad, Evan Bieske May 2013

Attaching Molecular Hydrogen To Metal Cations: Perspectives From Gas-Phase Infrared Spectroscopy, Viktoras Dryza, Berwyck Poad, Evan Bieske

Berwyck L. J. Poad

In this perspective article we describe recent infrared spectroscopic investigations of mass-selected M+–H2 and M+–D2 complexes in the gas-phase, with targets that include Li+–H2, B+–H2, Na+–H2, Mg+–H2, Al+–H2, Cr+–D2, Mn+–H2, Zn+–D2 and Ag+–H2. Interactions between molecular hydrogen and metal cations play a key role in several contexts, including in the storage of molecular hydrogen in zeolites, metal–organic frameworks, and …


A New Phase Unwrapping Algorithm Based On Three Wavelength Phase Shift Profilometry Method, Limei Song, Xiaoxiao Dong, Jiangtao Xi, Yanguang Yu, Chaokui Yang Dec 2012

A New Phase Unwrapping Algorithm Based On Three Wavelength Phase Shift Profilometry Method, Limei Song, Xiaoxiao Dong, Jiangtao Xi, Yanguang Yu, Chaokui Yang

Dr Yanguang Yu

Phase Shift Profilometry (PSP) method is widely used in 3D shape measurement. The advantage of the PSP method is that it is less sensitive to the surface reflectivity variations and the object can be measured point by point. But if only a single wavelength λ1 is used, the step height cannot be larger than λ1/4. In order to measure step height object, Gray Code (GC) and Multi-Wavelength Phase Shift Profilometry (MWPSP) method are used. But the GC method cannot solve the problem of the objects with a variety of colors under different illumination. The shortcoming of MWPSP …


Enhanced Molecular Chaperone Activity Of The Small Heat-Shock Protein Alphab-Cystallin Following Covalent Immobilization Onto A Solid-Phase Support, V Bellotti, Heath Ecroyd, J Carver, H J Griesser, B Thierry, J G Shapter, S S Griesser, S Giorgetti, M R Nussio, J A Gerrard, J Garvey Dec 2012

Enhanced Molecular Chaperone Activity Of The Small Heat-Shock Protein Alphab-Cystallin Following Covalent Immobilization Onto A Solid-Phase Support, V Bellotti, Heath Ecroyd, J Carver, H J Griesser, B Thierry, J G Shapter, S S Griesser, S Giorgetti, M R Nussio, J A Gerrard, J Garvey

Heath Ecroyd

The well-characterized small heat-shock protein, alphaB-crystallin, acts as a molecular chaperone by interacting with unfolding proteins to prevent their aggregation and precipitation. Structural perturbation (e.g., partial unfolding) enhances the in vitro chaperone activity of alphaB-crystallin. Proteins often undergo structural perturbations at the surface of a synthetic material, which may alter their biological activity. This study investigated the activity of alphaB-crystallin when covalently bound to a support surface; alphaB-crystallin was immobilized onto a range of solid material surfaces, and its characteristics and chaperone activity were assessed. Immobilization was achieved via a plasma-deposited thin polymeric interlayer containing aldehyde surface groups and reductive …